Nonadiabatic Molecular Dynamics Based on Trajectories

Entropy

Felipe Franco de Carvalho¹  Marine E. F. Bouduban¹  Basile F. E. Curchod¹ 

[1] Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland;

关键词: nonadiabatic dynamics;    trajectory surface hopping;    Ehrenfest dynamics;    Bohmian dynamics;    Born-Oppenheimer approximation;   

DOI  :  10.3390/e16010062

来源: mdpi

【 摘 要 】

Performing molecular dynamics in electronically excited states requires the inclusion of nonadiabatic effects to properly describe phenomena beyond the Born-Oppenheimer approximation. This article provides a survey of selected nonadiabatic methods based on quantum or classical trajectories. Among these techniques, trajectory surface hopping constitutes an interesting compromise between accuracy and efficiency for the simulation of medium- to large-scale molecular systems. This approach is, however, based on non-rigorous approximations that could compromise, in some cases, the correct description of the nonadiabatic effects under consideration and hamper a systematic improvement of the theory. With the help of an in principle exact description of nonadiabatic dynamics based on Bohmian quantum trajectories, we will investigate the origin of the main approximations in trajectory surface hopping and illustrate some of the limits of this approach by means of a few simple examples.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland